Influence of interdiffusion zones on the performance of coatings against coking and metal dusting

Metal Dusting

against coking and metal dustingC. Geers, M.C. Galetz, M. Schütze

e‐mail: geers@dechema.deFunded by: BMWi via AiF

Period: 01.01.2009 ‐ 31.12.2012

Functional Coating ApproachMetal Dusting Functional Coating Approach

A

B E FG

A‐C: catalytic mechanism of CO‐dissociation on a metal surface M = Fe Ni Co

uncoated low alloy steel (1%Cr; 0.4%Mo) after 100 hrs under metal dusting conditions at 650oC (H2‐24%CO‐2%H2O)

temperatures between 400 900oC

Metal Dusting Conditions

C

D

H

metal surface M = Fe, Ni, CoD: poisoning of the catalyzed dissociation by the use of 

tinE: schematic of epitaxial graphite nucleation 

caused by matching the crystallographic parameters of graphite with Fe3C and nickel

F: insertion of large elements disturbs epitaxyG: the poisoning  concept for high temperatures –

Ni3Sn2‐phase stable up to 1264oC

H: oxidation stability of intermetallic Ni‐Sn‐phases

temperatures between 400‐900oC atmospheres with high carbon 

activity aC ≥ 1;  low pO2

Metal Dusting Mechanisms

mechanism for ferritic steel

Coating Stability

The functional coating concept shown diffuse into the substrate transformations lead to stresses and reduce

iiiiii iv v

The functional coating concept shownabove relies on the constant chemicalcomposition of the coating during operationtime. Consequently, three different diffusionprocesses have to be controlled duringoperation time (i): no carbon is to diffusethrough the coating to the substrate alloy;no substrate components should diffuseinto the intermetallic coating; and nocoating components, especially tin, should

diffuse into the substrate.The Ni3Sn2‐phase is inert to carburization,coking and metal dusting. Carbon is not ableto diffuse through the coating.Nickel and iron from the substrate candiffuse into the intermetallic coating inalloys with a chromium content lower than15 wt%. This interdiffusion causes phasetransformations from Ni3Sn2 to Ni3Sn or(Ni3‐xFex)Sn2 with 0 < x < 1.5. These

transformations lead to stresses and reducethe coating stability.For substrates with a chromium contentgreater than 15 wt% the intermetallic nickel‐tin coating was found to be chemicallystable for more than 3000hrs (ii). This canbe associated with the high stability of theinterdiffusion zone as is described in thefollowing:

mechanism for nickel and nickel base alloys

The interdiffusion zone between the intermetallic coating and the

viivi

Overall composition of the  Composition of the h i i hsubstrate was intensively investigated for alloy 800, AISI 321 and alloy

600. For all three alloys, the interdiffusion zone was found to be adiffusion barrier consisting of chromium carbides, ‐phase as well asα‐ferrite for the austenites (viii). Figures ii, iii, iv and vi show this zonein a cross‐section of a nickel‐tin coated alloy 800 specimen after500 hrs exposure under metal dusting conditions at 620oC (H2‐24%CO‐2%H2O) produced using differential interference contrast (ii),electrochemically etched in 10M NaOH (iii), ZnSe‐PVD coated (iv).Figure vi shows the element maps measured using EPMA. In table vEPMA‐spot measurements of the positions highlighted as a)‐c) infigure iv are listed; a) matches the Cr23C6‐phase, b) ‐phase and c) α‐

interdiffusion zone found for a Ni‐Sn coated:

chromium rich precipitates in the interdiffusion zone ofNi‐Sn coated:

alloy 800

alloy 800

AISI 321

AISI 321alloy 600

This work is financially supported by the German Ministry of Economics via AiF under IGF contract no. 16294N which is gratefully 

acknowledged.

ferrite. The formation of these precipitates in the interdiffusion zoneoccurs due to the rapid depletion of nickel during the coating processin this zone. The nickel is consumed in the intermetallic nickel‐tincoating leaving behind an iron‐chromium rich layer (schematicallyshown in figure vii). This ‐phase rich layer was found to be a reliablediffusion barrier which stabilizes the chemical composition of theintermetallic coating for more than 3000hrs under metal dustingconditions.

650oC

viii